Characterization of mesoporous activated carbons prepared by pyrolysis of sewage sludge with pyrolusite

Activated carbons were prepared from sewage sludge by chemical activation. Pyrolusite was added as a catalyst during activation and carbonization. The influence of the mineral addition on the properties of the activated carbons produced was evaluated. The results show that activated carbons from pyrolusite-supplemented sewage sludge had up to a 75% higher BET surface area and up to a 66% increase in mesoporosity over ordinary sludge-based activated carbons. Batch adsorption experiments applying the prepared adsorbents to synthetic dye wastewater treatment yielded adsorption data well fitted to the Langmuir isotherm. The adsorbents from pyrolusite-supplemented sludges performed better in dye removal than those without mineral addition, with the carbon from pyrolusite-augmented sludge T2 presenting a significant increase in maximum adsorption capacity of 50 mg/g. The properties of the adsorbents were improved during pyrolusite-catalyzed pyrolysis via enhancement of mesopore production, thus the mesopore channels may provide fast mass transfer for large molecules like dyes.     

A study of boron adsorption onto activated sludge

Boron adsorption onto activated sludge was investigated using bench-scale reactors under simulated wastewater treatment conditions. Two experiments, continuous flow and batch, were performed. Boron concentrations were determined by means of inductively coupled plasma mass spectrometry. The results of the continuous-flow experiment indicated that a small amount of boron accumulated on the activated sludge and its concentration in the sludge depended on the nature of the biota in the sludge. Freundlich and Langmuir isotherm plots generated using the data from the batch experiment indicated that boron was adsorbed onto rather than absorbed into the sludge. The Freundlich constants, k and 1/n, were determined to be 26 mg/kg and 0.87. These values indicate that activated sludge has a limited capacity for boron adsorption and thus utilization of the excess sludge for farmland may not be toxic to plant at least boron concern.     

Activated carbons from waste biomass by sulfuric acid activation and their use on methylene blue adsorption

Preparation of the activated carbons from sunflower oil cake by sulphuric acid activation with different impregnation ratios was carried out. Laboratory prepared activated carbons were used as adsorbents for the removal of methylene blue (MB) from aqueous solutions. Liquid-phase adsorption experiments were conducted and the maximum adsorption capacity of each activated carbon was determined. The effects of various process parameters i.e., temperature, pH, initial methylene blue concentration, contact time on the adsorption capacity of each activated carbon were investigated. The kinetic models for MB adsorption onto the activated carbons were studied. Langmuir isotherm showed better fit than Freundlich isotherm for all activated carbon samples. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The separation factor (R(L)) revealed the favorable nature of the isotherm of the MB activated carbon system.     

Biosorption of a reactive dye (Rhodamine-B) from an aqueous solution using dried biomass of activated sludge

Low cost, locally available biomaterial was tested for its ability to remove reactive dyes from aqueous solution. Granules prepared from dried activated sludge (DAS) were utilized as a sorbent for the uptake of Rhodamine-B (Rh-B) dye. The effects of various experimental parameters (dye concentration, sludge concentrations, swelling, pretreatment and other factors) were investigated and optimal experimental conditions were ascertained. Nearly 15min was required for the equilibrium adsorption, and Rh-B dyes could be removed effectively. Dye removal performance of Rh-B and DAS increased with increasing concentrations. The acid pretreated biomass exhibited a slightly better biosorption capacity than alkali pretreated or non-pretreated biomass. The optimum swelling time for dye adsorption of the DAS within the swelling time range studied was 12h. Both the Freundlich and Langmuir isotherm models could describe the adsorption equilibrium of the reactive dye onto the activated sludge with the Langmuir isotherm showing the better agreement of the two. Second-order kinetic models confirmed the agreement.     

Removal of some polycyclic aromatic hydrocarbons from petrochemical wastewater using low-cost adsorbents of natural origin

Removal of polycyclic aromatic hydrocarbons (PAHs) from petrochemical wastewater was investigated using various low-cost adsorbents of natural origin including sugar cane bagasse, green coconut shells, chitin, and chitosan. Adsorption experiments of mixtures of PAHs (5.0-15.0 mg/L) have been carried out at ambient temperature (28+/-2 degrees C) and pH 7.5. The adsorption isotherms of PAHs were in agreement with a Freundlich model, while the uptake capacity of PAHs followed the order: green coconut shells>sugar cane bagasse>chitin>chitosan. The adsorption properties of green coconut shells were comparable to those of some conventional adsorbents such as Amberlite T. The partition coefficients in acetone:water, the adsorption constants at equilibrium, and the molecular masses of the PAHs could be linearly correlated with octanol-water partition coefficients.     

Removal of Cr(VI) from aqueous solutions by adsorption onto hazelnut shell activated carbon: kinetic and equilibrium studies

The adsorption Cr(VI) from aqueous solutions onto hazelnut shell activated carbon was carried out by varying the parameters such as pH, initial Cr(VI) concentration and temperature. The experimental data fitted well to the pseudo first-order kinetic model and then the rate constants were evaluated. The Langmuir isotherm provided the best correlation for Cr(VI) onto the activated carbon. Adsorption capacity was calculated from the Langmuir isotherm as 170 mg/g at an initial pH of 1.0 for the 1000 mg/l Cr(VI) solution. Thermodynamic parameters were evaluated and the adsorption is endothermic showing monolayer adsorption of Cr(VI).     

Dioxin-like polychlorinated biphenyl adsorbent obtained from enzymatic saccharification residue of lignocellulose

In this study, the effective utilization of lignocellulose residue as an adsorbent was investigated. Japanese cypress wood flour subjected to hydrothermal pretreatment and ball-mill grinding was saccharified with an enzyme. The residual wood flour was carbonized and activated by physical and chemical activation to produce adsorbents for persistent organic pollutant removal. The adsorption properties were investigated by pore analysis using the N₂ adsorption/desorption isotherm and adsorption tests for dioxin-like polychlorinated biphenyls in a hexane solution. The obtained adsorbents showed high production yields and adsorption properties for dioxin-like polychlorinated biphenyls.     

Application of a bioluminescence ATP assay in brewery wastewater treatment studies

The importance of having a rapid method for determining the viable biomass in activated-sludge wastewater treatment plants (WWTP) for process control and development is well recognized. The firefly bioluminescence ATP assay has been proposed for this purpose. Such an assay using partially purified firefly luciferase and synthetic firefly luciferin for the bioluminescence reaction, a liquid scintillation counter in the out-of-coincidence mode as luminescence detector, and a sludge ATP extraction technique involving dimethyl sulfoxide at room temperature is described. Experiments with several pure bacteria cultures were done to demonstrate the feasibility of applying this assay to activated sludge to activated sludge WWTP investigation and control. The ATP content of samples taken from various points in a 350000 gal/day brewery activated-sludge WWTP was monitored for 4.5 months. Good linear correlation between ATP and mixed-liquor suspended solids, return sludge suspended solids, and effluent suspended solids were observed. Percentage viabilities of the various sludge samples were derived from the ATP results.     

Enhanced adsorption of congo red from aqueous solutions by chitosan hydrogel beads impregnated with cetyl trimethyl ammonium bromide

The adsorption of congo red (CR) onto chitosan (CS) beads impregnated by a cationic surfactant (CTAB, cetyl trimethyl ammonium bromide) was investigated. Chitosan beads impregnated at a ratio of 1/20 of CTAB to CS (0.05% of CTAB and 1% of CS) increased the CR adsorption capacity by 2.2 times from 162.3 mg/g (0% CTAB) to 352.5 mg/g (0.05% CTAB). The CR adsorption decreased with an increase in pH of the CR solution from 4.0 to 9.0. The Sips isotherm model showed a good fit with the equilibrium experimental data and the values of the heterogeneity factor (n) indicated heterogeneous adsorption of CR onto CS/CTAB beads, as well as CS beads. The kinetic data showed better fit to the pseudo second-order rate model than to the pseudo first-order rate model. The impregnation of CS beads by cationic surfactants showed the highest adsorption capacities of CR compared to any other adsorbents and would be a good method to increase adsorption efficiency for the removal of anionic dyes in a wastewater treatment process.     

A novel approach for removing an industrial dye 4GL by an Algerian Bentonite

Adsorption processes of 4GL on two different bentonite-based sorbents were compared: i) Sodium-bentonite in the presence of a cationic surfactant CTAMB; ii) organobentonite alone. This latter was prepared by exchanging the inorganic cation of bentonite with a quaternary ammonium cation at 100% of the clay's CEC. Batch adsorption studies were conducted to evaluate the effect of various parameters such as the quaternary ammonium cation (CTAMB) loading, contact time and initial 4GL concentration.From the kinetic study, it is interesting to note that Organobentonite exhibits faster kinetics compared to Na-bentonite/CTAMB system. The comparison between isotherm plots makes clear that the presence of CTAMB in solution changes the 4GL isotherm. Compared to organobentonite, the adsorption capacity is higher when CTAMB was present in solution. In this case, the results of 4GL adsorption by bentonite obey to Langmuir model. While for organobentonite, all models seem to be applicable. The difference between the two methods is confirmed by XRD analysis.The performance shown by Organobentonite and Na-bentonite/CTAMB system was suitable compared to other adsorbents, reflecting a promising future utilization in wastewater treatment.     

Evaluation of two different Concanavalin A affinity adsorbents for the adsorption of glucose oxidase

Concanavalin A (Con A) was selected as ligand and thus immobilized onto two different supports, namely the polymeric Toyopearl and the inorganic silica, with the protection of its binding sites provided during the coupling procedure. The prepared Con A affinity adsorbents were then employed to evaluate their adsorption behaviour for the enzyme glucose oxidase (GOD). The immobilization kinetics showed that the immobilization of Con A on silica supports was much faster than that on Toyopearl supports, which could highly reduce the possibility of the denaturation of Con A. The optimal adsorption conditions for binding of GOD onto the ligand were determined in terms of the pH value and the ionic strength of the adsorption medium. The adsorption isotherms for binding GOD onto two Con A affinity adsorbents fitted well with the Langmuir equation. The maximum adsorption capacity q(m) of Toyopearl Con A and silica Con A were 7.9 mg/ml and 4.9 mg/ml, with a dissociation constant K(d) of 4.8 x 10(-7)M and 2.6 x 10(-6)M, respectively. Due to the less diffusive resistance, silica Con A showed both higher adsorption and desorption rates for GOD when compared with Toyopearl Con A. The nonspecific adsorption of GOD was less than 8% for both end-capped Toyopearl and silica supports. The dynamic adsorption of GOD for five times repeated processes showed a high stability for both prepared adsorbents. All the results indicate a good suitability of both Con A adsorbents for affinity adsorption of GOD.     

Adsorption of heavy metals onto sewage sludge-derived materials

Two materials were produced from sewage sludge by: (1) pyrolysis of dried sewage sludge (PS); (2) chemical activation of dried sewage sludge with ZnCl(2) followed by pyrolysis (AS). The aim was to study the application of these materials for metal purification from water and to determine the efficiency of each material. Although AS displayed higher capacity, both PS and AS were able to adsorb these metals and the preferential order was equal: Hg(II)>Pb(II)>Cu(II)>Cr(III). For each metal-adsorbent pair, metal adsorption was highly pH dependent. In all cases the equilibrium was well described both by the Langmuir and the Freundlich isotherms. At the corresponding optimum pH, AS showed the following adsorption capacities: 175.4, 64.1, 30.7 and 15.4 mg/g of Hg(II), Pb(II), Cu(II) and Cr(III), respectively. These results indicate the potential application of these sewage sludge based adsorbents for the treatment of metal polluted effluents.     

Adsorption of Neutral Red onto Mn-impregnated activated carbons prepared from Typha orientalis

Activated carbon was prepared from an inexpensive and renewable carbon source, Typha orientalis, by H(3)PO(4) activation and then impregnated with different Mn salts and tested for its Neutral Red (NR) adsorption capacities. The amount of Mn impregnated in the activated carbon was influenced by the anion species. Impregnation with Mn decreased the surface area, changed the pore size and crystal structure, and introduced more acidic functional groups such as carboxyl, lactone and phenol groups. The optimum adsorption performance for all the activated carbons was obtained at pH 3.7, Mn-Carbon dose of 0.100g/100ml solution and contact time 4.5h. The adsorption isotherms fit the Langmuir isotherm equation. The kinetic data followed the pseudo-second-order model. The thermodynamic parameters indicated that the processes were spontaneous and endothermic. According to these results, the prepared Mn modified activated carbons are promising adsorbents for the removal of Neutral Red from wastewater.     

Adsorption of dissolved Reactive red dye from aqueous phase onto activated carbon prepared from agricultural waste

The adsorption of Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from aqueous solution was investigated. Adsorption studies were carried out at different initial dye concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted; the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation. The effective diffusion coefficient was evaluated to establish the film diffusion mechanism. Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in accordance with poor desorption studies.     

Status of pathogens,antibiotic resistance genes and antibiotic residues in wastewater treatment systems

Pathogens are becoming nearly untreatable due to the rise in gaining new resistance against standard antibiotics. Coexistence of microbial pathogens, antibiotics and antibiotic resistant genes (ARGs) in wastewater treatment plants (WWTP) provide favourable conditions for the development of new antibiotic resistant bacteria (ARB); facilitate horizontal gene transfer among pathogens and may also serve as a hotspot for the spread of ARB and genes into the environment. In this study, the current status of wastewater treatment systems in the removal of pathogens, ARGs, and antibiotic residues are discussed. WWTP are efficient in removing pathogens and antibiotic residues to a greater extend during secondary and tertiary treatment processes. Recent studies, however, have shown high variations in the presence of pathogens including ARB as well as antibiotic resistance genes (ARG) in the final effluent. Prolonged sludge retention time (SRT) and hydraulic retention time (HRT) during secondary treatment will facilitate antibiotic removal by adsorption and biodegradation. However, the above conditions can also lead to the enhancement of antibiotic resistance process in microbes. Therefore, optimum conditions for the operation of conventional WWTP for the efficient removal of antibiotics are yet to be established. The removal of antibiotic residues can be accelerated by combining conventional activated sludge (CAS) process with an additional treatment technology involving dosing with ozone. The advanced biological treatment method using membrane bioreactors (MBR) in combination with coagulation reportedly has the best ARG removal efficiency, and removes both ARB and extracellular ARGs. While studies have predicted the fate for ARGs in wastewater treatment plants, the mechanisms of ARGs acquisition remains to be conclusively established. Thus, strategies to investigate the underlying mechanism of acquisition of ARGs within the WWTP are also provided in this review.     

Biosorption of reactive dyes by dried activated sludge: equilibrium and kinetic modelling

The biosorption of reactive dyes (Reactive Blue 2 - RB2 and Reactive Yellow 2 - RY2) onto dried activated sludge was investigated. The dye binding capacity of biosorbent was shown as a function of initial pH, initial dye concentration and type of dye. The equilibrium data fitted very well to both the Freundlich and Langmuir adsorption models. The results showed that both the dyes uptake processes followed the second-order rate expression.     

Improving the biotreatment of hydrocarbons-contaminated soils by addition of activated sludge taken from the wastewater treatment facilities of an oil refinery

Addition of activated sludge taken from the wastewater treatment facilities ofan oil refinery to a soil contaminated with oily sludge stimulated hydrocarbonbiodegradation in microcosms, bioreactors and biopile. Microcosms containing50 g of soil to which 0.07 % (w/w) of activated sludge was added presented ahigher degradation of alkanes (80 % vs 24 %) and polycyclic aromatic hydrocarbons(PAHs) (77 % vs 49 %) as compared to the one receiving only water, after 30days of incubation at room temperature. Addition of ammonium nitrate or sterilesludge filtrate instead of activated sludge resulted in a similar removal of PAHsbut not of alkanes suggesting that the nitrogen contained in the activated sludgeplays a major role in the degradation of PAHs while microorganisms of thesludge are active against alkanes. Addition of sludge also stimulated hydrocarbonbiodegradation in 10-kg bioreactors operated during 60 days and in a 50-m³ biopile operated during 126 days. This biopile treatment allowed the use of the soil for industrial purpose based on provincial regulation (``C' criteria). In contrast, the soil of the control biopile that received only water still exceeded C criteria for C₁₀–C₅₀ hydrocarbons, total PAHs, chrysene and benzo[a]anthracene.The stimulation effect of sludge was stronger on the 4-rings than on 2-rings PAHs.The soil of the biopile that received sludge was 4–5 times less toxic than the control. These results suggest that this particular type of activated sludge could be used to increase the efficiency of the treatment of hydrocarbon-contaminated soils in a biopile.     

Fate of polycyclic aromatic hydrocarbons during composting of activated sewage sludge with green waste

The level and fate of 16 polycyclic aromatic hydrocarbons (PAHs), targeted by the US Environmental Protection Agency (USEPA), has been studied over 90 days of composting of activated sludge with green waste, under a semi-arid climate. The total PAH calculated from the sum of the amounts of the 16 PAHs in the initial mixture of activated sludge and green waste, was lower than accepted European Union cut-off limits by about 0.48mgkg(-1). The treatment by composting led to a decrease of all PAHs mainly in the stabilization phase, but some differences could be observed between PAHs with three or fewer aromatic rings (N3) and those with four or more (N4). The former (except phenanthrene) exhibited a continuous decrease, while the latter PAHs with N of four or more and phenanthrene showed increases in the intermediate stages (30-60 days). This indicates the high potential sorption mainly of PAH with high molecular weight (N4) plus phenanthrene, their tight adsorption makes them inaccessible for microbial attack. The high molecular weight PAHs showed a greater reduction of their bioavailability than those of low molecular weight. Naphthalene, with the lowest molecular weight, showed the smallest decrease (about 67.8%) compared to other PAHs of higher molecular weight (decrease reaching 100%). This is in agreement with the fact that the adsorption is less reversible with increased numbers of fused aromatic rings or an increase of their hydrophobicity.     

Isotherm,Kinetic, and Thermodynamic Characteristics for Adsorption of 2,5-Xylenol onto Activated Carbon

The adsorption of the major tar compound, 2,5-xylenol, derived from the plant cell cultures of Taxus chinensis, onto activated carbon was examined at different initial 2,5-xylenol concentrations, durations, and temperatures. From the analysis of adsorption isotherms, the Langmuir isotherm model showed good fit to the equilibrium adsorption data. It was found that adsorption capacity decreased with increasing temperature, and the adsorption of 2,5-xylenol onto activated carbon was favorable. The obtained kinetic data for 2,5-xylenol adsorption with activated carbon agreed well with the pseudo-second-order kinetic model. By using intraparticle diffusion model, intraparticle diffusion and boundary layer diffusion did not play a dominant role in 2,5-xylenol adsorption. Thermodynamic parameters were calculated, which indicated that the adsorption was non-spontaneous, irreversible and exothermic nature. The isosteric heat of adsorption decreased with increase in surface loading, indicating a heterogeneous surface.     

Influence of polyaluminum chloride on microbial characteristics in anaerobic membrane bioreactors for sludge digestion

In this study, two parallel lab-scale anaerobic membrane bioreactors (AnMBRs), one of which was dosed with polyaluminum chloride (PAC) for membrane fouling control, were operated for treating excess activated sludge collected from a wastewater treatment plant (WWTP). The AnMBRs were inoculated with anaerobic digested sludge collected from an anaerobic digester of another WWTP. The microbial community of digested sludge and cake layer in AnMBRs, as well as that of excess sludge, was analyzed through polymerase chain reaction coupled with denaturing gradient gel electrophoresis (PCR-DGGE) and Illumina MiSeq. The dynamic variation of archaeal community in AnMBRs was not as obvious as that of bacterial community based on the PCR-DGGE results. Under the circumstance of stable operation, Cloacimonetes, Chloroflexi, Bacteroidetes, Proteobacteria, Firmicutes, and Ignavibacteriae were observed as the predominant phyla in digested sludge based on the Illumina results. In addition to that, the cake layer possessed similar predominant phyla with the digested sludge but owned a higher diversity. Furthermore, overlapping bacterial communities were discovered between the excess sludge and digested sludge. However, the abundance of aerobic bacteria was substantially reduced, while the abundance of anaerobic microorganisms like phylum Cloacimonetes and Smithella was enriched in digested sludge over time. Additional PAC dosing, on the one hand, affected the bioavailable substrate, thus further changing the microbial community structure; on the other hand, aluminum itself also affected specific microbial communities. Besides, PAC dosing indirectly influenced the bacterial diversity in AnMBR as well.